Rubber product and process of preparing same



Patented Mar. 22, 1932 TUNIT D SZTA TEQS, PATENT orrlcr.

1301mm) II. POWERS," or PENNS V GROVE, NEW J RSEY, nssrenon TO, I; I. DU your DE NEMOURS acomrnmr, or'wrrmmcromznnnAwimE, A, CORPORATION or DELA- especiallyadapted to accelerate, the vulcani- IWARE} 1T0 Drawing; l

and to the products obtained thereby More ing rubber and to a new class. of compounds -zation. V r The invention has amongits principalobjects the provision of aprocessiwhereby the time and temperature required for satisfactory vulcanization can beflessenedand the 'at- .tainnientofa rubber-product which of "superior quality and durability;

This applicatlon is in the n atureof a continuation, in part, of my Patent No. 1,7 32,582,

filed June 3, 1925 which-covers products re sulting from the interaction of. an aldehyde,

apriniary. amine, and carbon disulphide and v the employment of theseproducts as vulcanization accelerators. The accelerators de-, scribed herein area special type of the broad classofaccelerators described and claimed 1 intheparent application.

= I havenow discovered that if, the carbon bia, sulfide is causedito reaet with the amine first 1 and} the'resulting product then ,caused to rec act with the aldehyde that products particularly valuable-for use as accelerators are obtained. Also, I have discovered that those alcdehydes containing a; lurality of carbon zx iatoms are best adapted, ortheproductionof 5 accelerators of this type and thatpif certain ratios of: thethreecomponents, which ratios were not specifically disclosedinthe previous are of indefinite composition.

application, are employed, products, of; very t unusual activity; as accelerating agents re sult. 1 Particularly',:-I have discovered that i the use of two, three, four-or even five moles v offan aldehyde with onemole of amine gives compounds of remarkable activity. The amines and aldehydes used may be either alis phatic or. aromatic, although in the preferred embodiments of my invention I,-employ aliphatic aldehydes..; The compoundsresulting under a reflux'condenser, V fifty pounds of butyraldehyde is slowly added and the product heated under, pressure for three hours at 130 C. V The water is separated and the product/dried in vacuum. In

1 f A licatio skincare-4,1926. s m 1%. "1s9, 5ea.'

dithio c'arbamate is. formed: AQRNH,+cs ++nNHcssN1-nRjL dithio carbamate isheated under pressure with two or more moles of an aldehyde to' give, most probably, a condensation prod ,uct with the elimination of water The preparation of the new accelerators may be best disclosed'by the presentation of a number of examples embodyingthe invent10n.r It is to be understood that these exam- 1 ples are purely illustrative and thatthe coni l This-invention relates to an improved proc- When the amine andthe CS are mixed f-a 7 ess, for. treating rubber and similar materials diti'ons, reagents and proportions therein' s ecified are susceptible of variation. The

examples follow:

'Ewample J.-To two hundred and fifteen poundsof melted paratoluidine, one hundred pounds, ofrcarbon disulfide is slowly added Four hundred and a stock-of oneqhundred parts of smoked sheet, three parts of zinc oxide,:three and'a half parts'of; sulfur, and 0,37 5 parts of acI- celerator, agood cure was obtained in thirty minuteszat twenty five pounds steam pres.- sure.

Example 2. 11; 200 lbs. 0f aniline 1m slowly added "lbs; of carbon bisulfide;

The product, is cooled and "mixed until the reaction .is complete. 1000 lbs. of 'heptaldehyde are thenadded below the surface,cooling the mixture during the addition; The resulting product is heated under pressure at C; for three hours. 1 The resulting com: pound is'purified by distilling ofiu any unreacted; volatile materials'u'nder vacuum. t This 7 product, when tested apercentageofofi, in

. illustration definite quantities ofthe react 20,

a stock containing 100 parts of smoked sheet, 5 parts of zinc oxide, and 3 parts of sulfur, gave a good cure in 30 minutes at 25 lbs. steam pressure.

Example 3.l lbs. of carbon bisulfide are slowly added, under reflux, to 150 lbs. of butylamine, which has previously been cooled to 0 C. After the addition is complete 600 lbs. of butyraldehyde are rapidly added. The autoclave is closed and the mixture heated to 110 C. for2 hours, after which any un-v reacted volatile constituents are removed under vacuum. 7 This product, when tested in a percentage of 0.375, ina-stock containing100 parts of smoked sheet, -part's' of-zinc oxide,

and 3 parts of sulfur, gave a good cure in minutes at 25 lbs.'steam pressure. I

WVhile I have mentioned for purposes of ingcomponents and certain specific temperatures and times of reaction, and in general have given exact conditions under which my improved compounds may be made,.. I, of

course, do not limit myself to these specific proportions or conditions. These .illustrative conditions and methods of effecting the interaction and combination of the ingredients may obviously'be varied without departing from my invention. In certain cases I may use morethanonealdehyde and I may,

of course, use other aldehydes than those specified in the examples, also -more than one amine or a mixture OfELI'OIIlLtlC and aliphatic amines may be used. As little as one half a mole of carbon disulfide'foreach mole of amine may be employed.

In the claims where I specify an amine, I

intend to cover, also, the substituted-amines as the homologues of aniline. specify rubber I intend to cover all the botanical varieties of caoutchouc, which include hevea, balata, guttapercha, etc, and recognized substitutes therefor.

The vulcanization of the rubber compounds resulting from the employment of the new accelerator productsis efl'ected in less than the time normally required andthe re-' sulting rubber is of superior quality.

Iclaimz- 1. The process of treatingwrubber which comprises incorporating therewith, prior to vulcanization, the product obtained by causing carbon bisulfide to react with a primary aminefto. form anaddition compound and subsequently causing-this compound to further react with an aldehyde;

2.-=The process of treating, rubber which comprises incorporatingggtherewith, prior to V vulcanization, the productobtainedby caus ing carbon bisufide to react witha primary aromatic amine to form an addition com- .pound and subsequently. causing thiscompoundlto furtherreactfwith analdehyde.

3. The process oftreating rubberwhich: comprises incorporating therewith, prior; to

Where If pound and. subsequently causing this compound to further react with an aliphatic aldehyde containing a plurality of carbon atoms .notinexcess. of seven.

5. The process of treating rubber which comprises incorporating therewith, prior to vulcanization, the product obtained by causing carbon bisulfide to react with ;a primary aromatic amine to form an addition compound and subsequently causing this com-' pound to furtherreact with butyraldehyde.

6. The. process of "treating rubber which comprises incorporating therewith, prior to vulcanization, the product obtained by causing carbon bisulfide to react with aniline to form an addition compound and subsequently causing this compound to further react with butyraldehyde.

, 7. A rubber composition obtainable by in- I corporating with rubber a vulcanizing agent and the product obtained 'by causing analdehyde to react onthe' addition product of a primary aromatic amine and carbon bisulfide, and then vulcanizing.

8. A rubber composition obtainable by incorporating with rubber a-vulcanizing agent and the product obtained by causing analiphatic aldehyde containing not more than seven carbon atoms to react on the addition product of a primary aromatic amine and carbon bisulfide, and 'then vulcanizing;

9. A rubber composition obtainable-by incorporating with rubber a vulcanizing agent and the product obtained'by causing an aliphatic aldehyde containing a plurality of carbon atoms to reacton the addition product I of a primary aromatic annne and carbon bisulfide, and then vulcanizing.

10". A'rubb'er-composition obtainable by incorporating with=rubbera vulcanizing agent and the product-obtained by causing butyraldehyde toreact on the addition product of a primary aromatic amine and carbon. bisulfide, and then vulcanizing.

11. A rubber composition obtainable by incorporating. with rubber a vulcanizing agent and the product obtained by causing butyraldehyde to react on the addition product of aniline and carbon bisulfide,and then vulcanizing.

- 12. A rubber composition obtainable by incorporating with rubber a vulcanizing agent and an accelerator obtained by. causing from two to five moles ofbutyraldehydecto, :re

act on the reaction product of a mole of aniline and carbon bisulfide, and then vulcaniz- 1H0.

13. The process of treatingrubber which comprises incorporating therewith prior to vulcanization the product obtained by caus-,

ing carbon bisulfide to react with a compound of? the class comprising aniline, primary monoalkyl substituted phenylamines and primary alkyl amines and subsequently causing this compound to further react with a saturated straight chain aliphatic aldehyde containing not more than seven carbon atoms.

14.- A rubber composition obtainable by incorporating with rubber a yulcanizingagent it and a product obtained by causing a saturated straight chain aliphatic aldehyde containing.

(R.N.C.S.S.N.R) (OR) K said compound being obtained by causing carbon bisulfide to react with 1 mole of'an amine, p

incorporatmg with rubber a vulcanizmg of the class consisting of para toluidine, aniline, and butylamine to form an addition product, and subsequently causing the resulting product to react with from 2 to 5moles of a saturated straight chain aliphatic aldehyde containing not more than7 carbon atoms. c o p 16. The process of treating rubber whlch comprises incorporating therewith prior to vulcanization the product obtained by cansing carbon bisulfide to react with 1 mole of an amine of the class consisting of aniline and the mono-alkyl substituted phenylamines to form an addition product, and subsequently causing the resulting product. to react with from 2 to 5-moles of'avsaturated straight chain aliphatic aldehyde containing not more than 7 carbon atoms.

17. Theprocess of treating rubber which comprises incorporating therewith prior to and the mono-alkyl substituted phenylamines v to form an addition product, and subsequently causing the resulting. product to reactwith from 2 to 5 moles of an aliphatic aldehyde of the class consisting of butyraldehyde and 'heptaldehyde.

comprises incorporating therewith ing carbonbisulfide to react with 1 moleiof 19. The process of treating rubber which,

rior to vulcanization'the product obtained y cansan amine of the class consistingcof para vtoluidine, aniline, and c'butylamine to form anaddition product,'andsubsequently causing the resulting product to react with from 2 to 5 moles ofan aliphatic aldehyde of the class consisting of butyraldehyde and heptaldehyde. 5

20. The process oi treating rubber which comprises incorporating therewith, prior ,to vulcanization, the product obtained by causing carbon bisulfide to react with an; amine to form an addition compound and subsequently causing this compound to further reactwith analdehyde, twot01five moles of aldehyde being employed for everymole of,

amine. c

21; A process, such as covered byclaim 20, in which between three and five moles of am1ne.-

22. Arubber composition obtainable by aldehyde are employed for every mole of agent and an accelerator obtained by causing carbon bisulfide to react with an amine. to form an addition compound and subsequently causing this compoundto further react with an aldehyde, two to five molesof aldehyde being employed for every mole of amine, and then vulcanizing.

23. A rubber composition obtainable by incorporating with rubber a vulcanizing agent and an accelerator'obtained by causing carbon bisulfide toreact with an amine to form an additioncompound and subsequently causing this compound to further five moles of aldehyde being employed for every mole of amine, and then vulcanizing.

i In testimony whereof I afiix my signature.

DONALD POWERS vulcanization the product obtained by caus- 7 vulcanization the product obtained y causing carbon bisulfide to react with 1 mole of an .aminejof the class consistmg of .an llne react with an aldehyde, between three and" disc MAM, 

